Organoboron Derivatives of Stereoregular Phenylcyclosilsesquioxanes

Abstract

This study presents the synthesis of organoboron derivatives of stereoregular 4‐, 6‐, and 12‐unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70–80 %) and were fully characterized by 1H, 13C, 29Si, 11B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4‐(tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)phenyl) dimethylvinylsilane, was also confirmed by single‐crystal XRD.

Synthesis of Siloxane Derivatives of Phenylboronic Acids of Different Structures

“…Previously, in a study, 45 the synthesis of organoboron derivatives of stereoregular 4, 6, and 12 units of phenylcyclosilsesquioxanes via the hydrosilylation reaction was reported. In this case, the modifier had a pinacol-based protecting group.…”

“…To a stirred solution of (CH 3 ) 3 SiOSI­(H) (CH 3 )­OSi­(CH 3 ) 3 (0.10 g, 0.45 mmol, 1.3 equiv) in anhydrous toluene (2 mL) (dried according to the standard procedure), [4-(tetramethyl-1,3,2-dioxaborolan-2-yl)­phenyl]­dimethylvinylsilane (0.10 g, 0.35 mmol, 1 equiv) prepared according to the procedure in ref and Karstedt’s catalyst (3 μL; 0.09 mol %) was added per 1 equiv of the substrate. The reaction was carried out in an argon atmosphere for 12 h at room temperature.…”

Sequential hydrothiolation–hydrosilylation: a route to the creation of new organosilicon compounds with preset structures

“…This class of compounds makes it possible to obtain various functional derivatives and materials that can find application in various fields of chemistry and materials science. 54–64…”

“…This class of compounds makes it possible to obtain various functional derivatives and materials that can find application in various fields of chemistry and materials science. [54][55][56][57][58][59][60][61][62][63][64] Thus, we chose stereoregular organocyclosilsesquioxane 20 as the starting compound (Fig. 6).…”

The Use of the Thiol-Ene Addition Click Reaction in the Chemistry of Organosilicon Compounds: An Alternative or a Supplement to the Classical Hydrosilylation?

“…Shchegolikhina’s team is actively developing the synthesis of stereoregular organosiloxanes, a unique class of organosilicon compounds [ 93 , 94 , 95 ]. These compounds are synthesized from polyhedral metallosiloxanes and cannot be obtained by the classical organosilicon chemistry reactions.…”